Etching composition and method for fabricating semiconductor device by using the same

ABSTRACT

An etching composition selectively removes a titanium nitride film from a stacked conductive film structure including a titanium nitride (TiN) film and a tantalum nitride (TaN) film. The etching composition configured to etch titanium nitride (TiN) includes 5 wt % to 30 wt % of hydrogen peroxide, 15 wt % to 50 wt % of acid compound, and 0.001 wt % to 5 wt % of corrosion inhibitor, with respect to a total weight of the etching composition, wherein the acid compound includes at least one of phosphoric acid (H 3 PO 4 ), nitric acid (HNO 3 ), hydrochloric acid (HCl), hydroiodic acid (HI), hydrobromic acid (HBr), perchloric acid (HNO 4 ), silicic acid (H 2 SiO 3 ), boric acid (H 3 BO 3 ), acetic acid (CH 3 COOH), propionic acid (C 2 H 5 COOH), lactic acid (CH 3 CH(OH)COOH), and glycolic acid (HOCH 2 COOH).

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority from Korean Patent Application No.10-2016-0160023 filed on Nov. 29, 2016 in the Korean IntellectualProperty Office, and all the benefits accruing therefrom under 35 U.S.C.119, the contents of which in its entirety are herein incorporated byreference.

BACKGROUND 1. Technical Field

Some example embodiments of the present disclosure relates to an etchingcomposition and a method for fabricating a semiconductor device by usingthe same, and more specifically, to an etching composition toselectively remove titanium nitride (TiN) on a conductive film, and amethod for fabricating a semiconductor device by using the same.

2. Description of the Related Art

The recent dramatic increase in the distribution of information mediahas led to remarkable advancement in the functionalities ofsemiconductor devices. To ensure higher competitiveness, newsemiconductor products are required to meet demands for lower costs andhigher quality by way of higher integration. The semiconductorscale-down continues to achieve higher integration.

To achieve scale-down of a semiconductor device, a high-k insulatingfilm is used. Further, to reduce or prevent the Fermi level pinning, ametal material having a proper work function is used as a gate electrodeon the high-k insulating film. The gate electrode, which includes ametal material, may include titanium-based materials (e.g., titanium(Ti) and titanium nitride (TiN)) or tantalum-based materials (e.g.,tantalum (Ta) and tantalum nitride (TaN)).

An optimum or desirable work function for a metal gate electrode variesbetween a NMOS transistor and a PMOS transistor. Accordingly, when asame material is used for the metal gate electrodes of the NMOS and PMOStransistors, one gate electrode of the NMOS and PMOS transistors may notexhibit a desired work function. The gate electrode of the NMOStransistor may use a different material and/or a different filmstructure from the gate electrode of the PMOS transistor. To implementdifferent work functions from each other, titanium nitride and tantalumnitride may be used in the gate electrode.

SUMMARY

Some example embodiments of the present disclosure provide an etchingcomposition to selectively remove a titanium nitride film from a stackedconductive film structure including a titanium nitride (TiN) film and atantalum nitride (TaN) film.

Other example embodiments of the present disclosure provide a method forfabricating a semiconductor device using an etching composition toselectively remove a titanium nitride film from a stacked conductivefilm structure including the titanium nitride film and the tantalumnitride film.

The present disclosure is not limited to the example embodiments setforth above and example embodiments other than those set forth abovewill be clearly understood to a person skilled in the art from thefollowing description.

According to an example embodiment of the present inventive concepts, anetching composition configured to etch titanium nitride (TiN) includeswith respect to a total weight of the etching composition, 5 wt % to 30wt % of hydrogen peroxide, 15 wt % to 50 wt % of acid compound, and0.001. wt % to 5 wt % of corrosion inhibitor, wherein the acid compoundcomprises at least one of phosphoric acid (H₃PO₄), nitric acid (HNO₃),hydrochloric acid (HCl), hydroiodic acid (HI), hydrobromic acid (HBr),perchloric acid (HClO₄), silicic acid (H₂SiO₃), boric acid (H₃BO₃),acetic acid (CH₃COOH), propionic acid (C₂H₅COOH), lactic acid(CH₃CH(OH)COOH), and glycolic acid (HOCH₂COOH).

According to another example embodiment of the present inventiveconcepts, an etching composition configured to etch titanium nitride(TiN includes hydrogen peroxide, acid compound, and corrosion inhibitor,wherein a ratio of a weight of the acid compound with respect to aweight of the hydrogen peroxide is from 1 to 7, and the acid compoundcomprises at least one of phosphoric acid (H₃PO₄), nitric acid (HNO₃),hydrochloric acid (HCl), hydroiodic acid (HI), hydrobromic acid (HBr),perchloric acid (HClO₄), silicic acid (H₂SiO₃), boric acid (H₃BrO₃),acetic acid (CH₃COOH), propionic acid (C₂H₅COOH), lactic acid(CH₃CH(OH)COOH), and glycolic acid (HOCH₂COOH).

According to still another example embodiment of the present inventiveconcepts, a method for fabricating a semiconductor device includesforming an interlayer insulating film including a first trench and asecond trench; forming a first TaN film along a sidewall and a bottomsurface of the first trench, and forming a second TaN film along asidewall and a bottom surface of the second trench; forming a first TiNfilm on the first TaN film and a second TiN film on the second TaN film;forming a mask pattern on the second TiN film; and exposing the firstTaN film by removing the first TiN film with wet etching by using themask pattern, wherein the wet etching uses an etching composition, theetching composition comprises 5 wt % to 30 wt % of hydrogen peroxide, 15wt % to 50 wt % of acid compound, and 0.001 wt % to 5 wt % of corrosioninhibitor, with respect to a total weight of the etching composition,and the acid compound comprises at least one of phosphoric acid (H₃PO₄),nitric acid (HNO₃), hydrochloric acid (HCl), hydroiodic acid (HI),hydrobromic acid (HBr), perchloric acid (HClO₄), silicic acid (H₂SiO₃),boric acid (H₃BO₃), acetic acid (CH₃COOH), propionic acid (C₂H₅COOH),lactic acid (CH₃CH(OH)COOH), and glycolic acid (HOCH₂COOH).

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other features and advantages of the present disclosurewill become more apparent to those of ordinary skill in the art bydescribing in detail example embodiments thereof with reference to theaccompanying drawings.

FIGS. 1 to 14 are views illustrating intermediate stages of fabricationillustrating a method for fabricating a semiconductor device by using anetching composition according to some example embodiments of the presentdisclosure.

FIGS. 15 to 25 are views illustrating intermediate stages of fabricationillustrating a method for fabricating a semiconductor device by using anetching composition according to some example embodiments of the presentdisclosure.

DETAILED DESCRIPTION

The term “alkyl” represents an aliphatic hydrocarbon group. The alkylpart may be a “saturated alkyl group,” representing that any alkene oralkyne part is not included. The alkyl part may be also an “unsaturatedalkyl part,” representing that at least one alkene or alkyne part isincluded. The “alkene” part represents a group in which at least twocarbon atoms are formed with at least one carbon-carbon double bond, andthe “alkyne” part represents a group in which at least two carbon atomsare formed with at least one carbon-carbon triple bond.

The alkyl group may be substituted or unsubstituted. When beingsubstituted, a substituted group is one or more groups separately andindependently selected from amino, including cycloalkyl, aryl,heteroaryl, heteroalicyclic, hydroxy, alkoxy, aryloxy, mercapto,alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamyl,N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, N-amido,S-sulfonamido, N-sulfonamido, C-carboxy, O-carboxy, isocyanato,thiocyanate, isothiocyanate, nitro, silyl, trihalomethanesulfonyl, aminoincluding mono- and de-substituted amino groups, and protectedderivatives thereof. A typical alkyl group may include methyl, ethyl,propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl,ethenyl, prophenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, etc., but not limited hereto.

For example, an etching composition to be described below may be anetching solution to etch titanium nitride.

For another example, the etching composition to be described below maybe an etching solution to selectively remove a titanium nitride filmfrom a stacked film of a titanium nitride film and a tantalum nitridefilm.

The etching composition according to some example embodiments mayinclude hydrogen peroxide (H₂O₂), acid compound, corrosion inhibitor,and solvent.

The titanium nitride film is selectively removed from the layered filmof the titanium nitride film and the tantalum nitride film using theetching composition.

The etching composition includes hydrogen peroxide. Hydrogen peroxidemay be used as oxidizing agent.

Hydrogen peroxide may oxidize the titanium nitride film. That is,hydrogen peroxide may change the titanium nitride film into the titaniumoxide film.

The etching composition may include 5 wt % to 30 wt % of hydrogenperoxide with respect to a total weight of the etching composition. Forexample, the etching composition may include 12 wt % to 30 wt % ofhydrogen peroxide with respect to a total weight of the etchingcomposition. For example, the etching composition may include 15 wt % to25 wt % of hydrogen peroxide with respect to a total weight of theetching composition.

When hydrogen peroxide is less than the range mentioned above, thetitanium nitride film may not he sufficiently oxidized. Accordingly, theetch rate of the titanium nitride film may be lowered.

When hydrogen peroxide exceeds the range mentioned above, oxidizationmay occur on other films (e.g., tantalum nitride film) as well astitanium nitride film. In example embodiments, etch selectivity of thetantalum nitride film with respect to the titanium nitride film may belowered.

The etching composition may include the acid compound. The acid compoundmay adjust pH of the etching composition.

The acid compound may include organic acid or inorganic acid. The acidcompound may include, for example, at least one of phosphoric acid(H₃PO₄), nitric acid (HNO₃). hydrochloric acid (HCl), hydroiodic acid(HI), hydrobromic acid (HBr), perchloric acid (HClO₄), silicic acid(H₂SiO₃), boric acid (H₃BO₃), acetic acid (CH₃COOH), propionic acid(C₂H₅COOH), lactic acid (CH₃CH(OH)COOH), and glycolic acid (HOCH₂COOH).

In the etching composition according to some example embodiments, theacid compound may include phosphoric acid. For example, the acidcompound may be phosphoric acid.

In the etching composition according to some example embodiments, theacid compound may not include a sulfur-based compound. As used herein,statement “(does) not include sulfur-based compound” does notnecessarily mean that the etching composition does not include a sulfurion.

When the etching composition includes sulfuric acid and hydrogenperoxide, Caro's acid (H₂SO₅) may be formed from a reaction betweensulfuric acid and hydrogen peroxide. Caro's acid formed as describedabove may excessively etch the tantalum nitride film as well as etchingthe titanium nitride film. That is, when sulfuric acid is included inthe etching composition, side reaction may occur tantalum nitride filmis over-etched as well as the titanium nitride film.

The etching composition may include 15 wt % to 50 wt % of the acidcompound with respect to a total weight of the etching composition. Forexample, the etching composition may include 20 wt % to 40 wt % of theacid compound with respect to a total weight of the etching composition.

When the acid compound is less than the range mentioned above, theetching of the titanium nitride film may not sufficiently occur.Accordingly, etch rate of the titanium nitride film may be lowered.

When the acid compound exceeds the range mentioned above, other films(e.g., tantalum nitride film) may be considerably etched as well as thetitanium nitride film. In such case, etch selectivity of the tantalumnitride film with respect to the titanium nitride film may be lowered.

The etching composition may include the corrosion inhibitor. Thecorrosion inhibitor may be adsorbed onto films other than the etchedfilm, thus preventing or reducing the films other than the etched filmbeing etched with etching composition.

For example, the corrosion inhibitor may include at least one ofammonium peroxysulfate, ammonium sulfate, monoammonium phosphate,diammonium phosphate, tri ammonium phosphate, ammonium chloride,ammonium acetate, ammonium carbonate, ammonium nitrate, ammonium iodide,1,2,4-triazole, 3-aminotriazole, 5-aminotetrazole, benzotriazole,pyrazole, imidazole, ascorbic acid, citric acid, succinic acid, maleicacid, malonic acid, thioglycolic acid, tannic acid, methyl gallate,ethyl gallate, and propyl gallate.

At least part of the corrosion inhibitor may include a nitrogen atomhaving noncovalent electron pairs, but not limited hereto. Using thenoncovalent electron pairs, the corrosion inhibitor may be adsorbed ontoother films other than the etched film to reduce or prevent the otherfilms other than the etched film from being etched.

Ammonium hydroxide may include the noncovalent electron pairs, but thecorrosion inhibitor may not include ammonium hydroxide. Ammoniumhydroxide is a basic material. When the etching composition includesammonium hydroxide, pH of the etching composition may be elevated.Accordingly, etching of the titanium nitride film may not sufficientlyoccur.

The etching composition may include 0.001 wt % to 5 wt % of thecorrosion inhibitor with respect to a total weight of the etchingcomposition.

When the corrosion inhibitor is less than the range mentioned above, asurface of the tantalum oxide film, which is the oxidized tantalumnitride film or tantalum nitride film, may not be protected.

When the corrosion inhibitor exceeds the range mentioned above, thecorrosion inhibitor may be adsorbed strongly onto the surface of thefilm to the extent that it may not be removed in a subsequent cleanprocess. The unremoved corrosion inhibitor may affect the subsequentprocess.

The etching composition may include a remainder of solvent. The solventmay be, for example, deionized water. The solvent may be added to theetching composition such that the etching composition may be 100 wt %.

With respect to a total weight of the etching composition, the etchingcomposition may include 15 wt % to 79 wt % of the solvent.

In the etching composition according to some example embodiments, of theetching composition may be less than or equal to 2.

According to some example embodiments, the etching composition mayfurther include a chelating agent.

The chelating agent may include, for example, at least one ofethylenediaminetetraacetic acid, iminodiacetic acid,diethylenetriaminepentaacetic acid, glycine, alanine, valine, leucine,isoleucine, serine, threonine, tyrosine, phenylalanine, tryptophane,aspartic acid, glutamic acid, glutamine, asparagine, lysine, arginine,histidine, hydroxylysine, cysteine, methionine, cystine, proline,sulfamic acid, and hydroxyproline.

When the etching composition includes the chelating agent, the etchingcomposition may include 0.001 wt % to 5 wt % of the chelating agent withrespect to a total weight of the etching composition.

According to some example embodiments, the etching composition mayfurther include a surfactant.

The surfactant may include, for example, at least one of alkylsulfonate, ammonium alkyl sulfonate, alkyl ether sulfonate, alkyl arylether sulfonate, alkyl phosphate, ammonium alkyl phosphate, alkyl etherphosphate, alkyl aryl ether phosphate, fluoroalkyl sulfonimide, ammoniumfluoroalkyl sulfonimide, C_(n)H_(2n+1)CH₂CH₂SO³⁻NH₄₊,C_(n)H_(2n+1)CH₂CH₂SO₃H, (C_(n)H_(2n+1)CH₂CH₂O)xPO(ONH₄₊)y(OCH₂CH₂OH)z,C_(n)H_(2n+1)CH₂CH₂O(OCH₂CH₂OH)xH, C_(n)H_(2n+1)SO₂N(C₂H₅)(CH₂CH₂)xH,C_(n)H_(2n+1)CH₂CH₂OCH₂(OH)CH₂CH₂N(C_(n)H_(2n+1))₂,C_(n)H_(2n+1)CH₂CH₂OCH₂(OCH₂CH₂)_(n)CH₂CH₂N(C_(n)H_(2n+1))₂,C_(n)F_(2n+1)CH₂CH₂SO³⁻NH₄₊, C_(n)F_(2n+1)CH₂CH₂SO₃H,(C_(n)F_(2n+1)CH₂CH₂O)xPO(ONH₄₊)y(OCH₂CH₂OH)z,C_(n)F_(2n+1)CH₂CH₂O(OCH₂CH₂OH)xH, C_(n)F_(2n+1)SO₂N(C₂H₅)(CH₂CH₂xH,C_(n)F_(2n+1)CH₂CH₂OCH₂(OH)CH₂CH₂N(C_(n)F_(2n+1))₂, andC_(n)F_(2n+1)CH₂CH₂OCH₂(OCH₂CH₂)_(n)CH₂CH₂N(C_(n)F_(2n+1))₂.

In the above chemical formula, n is an integer from 1 to 20, when x, yand z are present simultaneously, x, y and z are real numbers satisfyingx+y+z=3, and when x is present alone, x is an integer of 1 to 3.

When the etching composition includes the surfactant, the etchingcomposition may include 0.001 wt % to 0.1 wt % of the surfactant withrespect to a total weight of the etching composition.

When the surfactant is less than 0.001 wt %, due to a relatively lowsurfactant content adsorbed onto the surface of the tantalum nitridefilm, its role of reducing an etch rate of the tantalum nitride film maybe insufficient. Further, because it is difficult to reduce surfacetension of the titanium nitride film, it may not be possible toeffectively increase etch rate of the titanium nitride film.

When the surfactant exceeds 0.1 wt %, it is not economical to use anexcess amount of surfactant because the resultant effects are samewithin the range mentioned above. Further, an excess amount ofsurfactant may generate excessive foams, resulting in a difficulty inutilization of the etching composition.

According to some example embodiments, the etching composition mayfurther include a sequestering agent, etc.

For example, in the etching composition of the present disclosure, aratio of weight of the acid compound to a weight of hydrogen peroxidemay be 1 to 7. That is, in the etching composition of the presentdisclosure, a weight of the acid compound may be substantially the sameas a weight of hydrogen peroxide, or a weight of the acid compound maybe less than or equal to seven times the weight of hydrogen peroxide.

For another example, in the etching composition of the presentdisclosure, a weight of hydrogen peroxide may be greater than a weightof the acid compound.

In the etching composition according to some example embodiments, etchselectivity of the titanium nitride film to the tantalum nitride filmmay be equal to or greater than 500. For example, etch selectivity ofthe titanium nitride film to the tantalum nitride film may be equal toor greater than 1,000. For example, etch selectivity of the titaniumnitride film to the tantalum nitride film may be from 1,500 to 5,000.

In one example, when the tantalum nitride film is removed by a thicknesst and the titanium nitride film is removed by a thickness 2000t for thesame duration of time, etch selectivity of the titanium nitride film tothe tantalum nitride film may be 2000.

The etching composition according to some example embodiments mayinclude a fluorine-containing compound or may not include the same.

For example, when the titanium nitride film is removed using the etchingcomposition of the present disclosure in an environment where the oxideis exposed, the etching composition according to some exampleembodiments may not include the fluorine-containing compound.

For another example, when the titanium nitride film is removed using theetching composition of the present disclosure in an environment wherethe oxide is not exposed, the etching composition according to someexample embodiments may include the fluorine-containing compound.

Although it is described above that exposure of the oxide determineswhether or not the etching composition includes the fluorine-containingcompound, the example embodiments are not limited hereto.

When wet etching is performed using the etching composition according tosome example embodiments, wet etching temperature may be between 20° C.and 100° C., for example, although example embodiments are not limitedhereto.

Following will explain the etching composition according to some exampleembodiments using experimental examples. However, the followingexperimental examples are provided only for the purpose of explanation,and the present disclosure is not limited hereto.

In the following experimental examples, the composition of the etchingcomposition are expressed with wt % for clear representation of therelative amounts. Accordingly, one of ordinary skilled in the art whonormally understands the present disclosure will be able to repeat andimplement the experiments by properly adjusting a scale based on wt %amount suggested herein.

Following table represents composition of the etching compositionincluded in the experimental examples, with etch rate of the titaniumnitride film using the same, and etch rate of the tantalum nitride film.Further, the following table represents etch selectivity of the titaniumnitride film with respect to the tantalum nitride film of the etchingcomposition included in the experimental examples.

Experimental examples A to T represent the etching compositionsaccording to some example embodiments, and Experimental examples U to ABrepresent comparative examples.

The compositions of the etching compositions are expressed with wt % ofeach component with respect to a total weight of the etchingcomposition. The etching compositions of Experimental examples A to Tinclude hydrogen peroxide, acid compound, corrosion inhibitor, anddeionized water (DIW) as a remainder of the solvent.

Substrates formed with the titanium nitride film and the tantalumnitride film were immersed into the etching composition of Experimentalexamples A to AB. The substrate formed with the titanium nitride filmwas immersed into the etching composition for 30 seconds, and thesubstrate formed with the tantalum nitride film was immersed into theetching composition for 3 minutes.

To obtain etch rates of the titanium nitride film and the tantalumnitride film immersed in the etching composition, change in a filmthickness was measured using Ellipsometer (SE-MG-1000). Using the changein the film thickness and the immersion time, etch rates of the titaniumnitride film and the tantalum nitride film were determined. The unit ofthe etch rates of the titanium nitride film and the tantalum nitridefilm is Å/min. Etch selectivity of the titanium nitride film withrespect to the tantalum nitride film was determined by dividing the etchrate of the titanium nitride film by the etch rate of the tantalumnitride film.

The unit of temperature for the evaluation of the wet etching performedfor the evaluation of etch rates of the titanium nitride film and thetantalum nitride film using the etching composition of the experimentalexamples may be ° C.

The etch rate of the tantalum nitride film in Experimental examples A toT was marked less than 0.1 Å/min, because it exhibited an etch ratelower than a range that can be measured using the measurement equipment(i.e., Ellipsometer). However, for the sake of calculation of the etchselectivity in Experimental examples A to T, etch rate of the tantalumnitride film was given as 0.1 Å/min.

‘3-ATZ’ of the experimental examples represents ‘3-aminotriazole,’ ‘PG’represents ‘propyl gallate’, ‘AN’ represents ‘ammonium nitrate,’ ‘APS’represents ‘ammonium persulfate,’ and ‘TMAH’ represents‘tetramethylammonium hydroxide.’

Etching Rate Selectivity Formulation Composition Temperature TiN TaNTiN/TaN A 20 wt % hydrogen peroxide, 30 wt % 70 275 <0.1 2750 phosphoricacid, 2 wt % 3-ATZ, 48 wt % DIW B 20 wt % hydrogen peroxide, 30 wt % 70260 <0.1 2600 phosphoric acid, 2 wt % PG, 48 wt % DIW C 20 wt % hydrogenperoxide, 30 wt % 70 248 <0.1 2480 phosphoric acid, 2 wt % AN, 48 wt %DIW D 20 wt % hydrogen peroxide, 30 wt % 70 282 <0.1 2820 phosphoricacid, 2 wt % APS, 48 wt % DIW E 25 wt % hydrogen peroxide, 15 wt % 70300 <0.1 3000 phosphoric acid, 2 wt % APS, 58 wt % DIW F 12 wt %hydrogen peroxide, 50 wt % 70 200 <0.1 2000 phosphoric acid, 2 wt % APS,36 wt % DIW G 20 wt % hydrogen peroxide, 20 wt % 70 225 <0.1 2250phosphoric acid, 2 wt % APS, 58 wt % DIW H 20 wt % hydrogen peroxide, 40wt % 70 285 <0.1 2850 phosphoric acid, 2 wt % APS, 38 wt % DIW I 15 wt %hydrogen peroxide, 30 wt % 70 254 <0.1 2540 phosphoric acid, 2 wt % APS,53 wt % DIW J 25 wt % hydrogen peroxide, 30 wt % 70 326 <0.1 3260phosphoric acid, 2 wt % APS, 43 wt % DIW K 20 wt % hydrogen peroxide, 50wt % 70 336 <0.1 3360 phosphoric acid, 2 wt % APS, 28 wt % DIW L  5 wt %hydrogen peroxide, 30 wt % 70 50 <0.1 500 phosphoric acid, 2 wt % APS,63 wt % DIW M 10 wt % hydrogen peroxide, 30 wt % 10 130 <0.1 1300phosphoric acid, 2 wt % APS, 58 wt % DIW N  5 wt % hydrogen peroxide, 30wt % acetic 70 39 <0.1 390 acid, 2 wt % APS, 63 wt % DIW P 15 wt %hydrogen peroxide, 30 wt % acetic 70 141 <0.1 1410 acid, 2 wt % APS, 53wt % DIW Q 20 wt % hydrogen peroxide, 30 wt % acetic 70 150 <0.1 1500acid, 2 wt % APS, 48 wt % DIW R 25 wt % hydrogen peroxide, 30 wt %acetic 70 181 <0.1 1810 acid, 2 wt % APS, 43 wt % DIW S 20 wt % hydrogenperoxide, 30 wt % phosphoric acid, 2 wt % nitric acid, 2 wt % 70 288<0.1 2880 APS, 46 wt % DIW T 20 wt % hydrogen peroxide, 30 wt %phosphoric acid, 3 wt % nitric acid, 2 wt % 70 320 <0.1 3200 APS, 45 wt% DIW U 25 wt % hydrogen peroxide, 75 wt % DIW 70 150 1.4 107 V 31 wt %hydrogen peroxide, 69 wt % DIW 70 366 2.4 153 W 25 wt % hydrogenperoxide, 2 wt % TMAH, 0.2 50 264 3.3 79 wt % hydrazine, 72.8 wt % DIW X25 wt % hydrogen peroxide, 2 wt % hydrazine, 50 330 3.3 99 73 wt % DIW Y20 wt % hydrogen peroxide, 30 wt % sulfuric 70 398 3.3 121 acid, 2 wt %APS, 48 wt % DIW Z 25 wt % hydrogen peroxide, 1 wt % NH4OH, 50 266 5.846 74 wt % DIW AA 50 wt % nitric acid, 0.1 wt % HF, 49.9 wt % DIW 50 1075.1 21 AB 20 wt % hydrogen peroxide, 10 wt % 70 180 0.7 257 phosphoricacid, 2 wt % APS, 68 wt % DIW

In the experimental example using hydrogen peroxide only or using TMAHinstead of acid compound according to some example embodiments, it wasobserved that the tantalum nitride film was etched and damaged.Accordingly, it was confirmed that etch selectivity of the titaniumnitride film with respect to the tantalum nitride film was alsodeteriorated.

In experimental examples A to T including the etching compositionsaccording to some example embodiments, it was observed that the etchrate of the tantalum nitride film was low, and accordingly, damage ofthe tantalum nitride film was low. Accordingly, it was confirmed thatthe etch selectivity of the titanium nitride film with respect to thetantalum nitride film was relatively high.

A method for fabricating a semiconductor device using the etchingcomposition according to some example embodiments describes amulti-channel transistor including multi-channel (e.g., fin-typetransistor (FinFET)) including a fin-type pattern of a channel region, atransistor including nanowire, and a transistor including a nanosheet),but a planar transistor may be also implemented.

Further, the method for fabricating the semiconductor device using theetching composition according to some example embodiments describesfabrication of the transistor, but the method may be also applied tofabrication of wires in a back-end-of-line (BEOL) process connected tothe transistor.

FIGS. 1 to 14 are views illustrating intermediate stages of fabricationillustrating a method for fabricating a semiconductor device using anetching composition according to some example embodiments of presentdisclosure. FIG. 4 is a cross sectional view taken on lines A-A and C-Cof FIG. 3, and FIG. 5 is a cross sectional view taken on lines B-B andD-D of FIG. 3.

Referring to FIG. 1, a first fin-type pattern 110 and a second fin-typepattern 210 may be farmed on the substrate 100. The first fin-typepattern 110 may be formed in a first region I, and the second fin-typepattern 210 may be formed in a second region II.

The substrate 100 may include the first region I and the second regionII. The first region I and the second region II may be the regionsspaced apart from each other, or regions connected to each other.Further, the transistor formed in the first region I may have the same,or different conductivity type as that of the transistor formed in thesecond region II,

The substrate 100 may be a bulk silicon or a silicon-on-insulator (SOI).Alternatively, the substrate 100 may be a silicon substrate, or mayinclude other materials such as silicon germanium, silicon germanium oninsulator (SGOI), indium antimonide, lead telluride, indium arsenide,indium phosphide, gallium arsenide, or gallium antimonide, but limitednot hereto.

The first fin-type pattern 110 may be elongated in a first direction X1,and the second fin-type pattern 210 may be elongated in a seconddirection X2. The first fin-type pattern 110 and the second fin-typepattern 210 may be a part of the substrate 100, and may include anepitaxial layer grown from the substrate 100.

The first fin-type pattern 110 and the second fin-type pattern 210 mayeach include, for example, an element semiconductor material such assilicon or germanium. Further, the first fin-type pattern 110 mayinclude a compound semiconductor such as IV-IV group compoundsemiconductor or group compound semiconductor. Specifically, take theIV-IV group compound semiconductor as an example, the first fin-typepattern 110 and the second fin-type pattern 210 may be a binary compoundor a ternary compound including at least two or more of carbon (C),silicon (Si), germanium (Ge) and tin (Sn), or these compounds doped withIV group element. Take the III-V group compound semiconductor as anexample, the first fin-type pattern 110 and the second fin-type pattern210 may be one of a binary compound, a ternary compound or a quaternarycompound which is formed by a combination of a III group element, whichmay be at least one of aluminum (Al), gallium (Ga), or indium (In), anda V group element, which may be one of phosphorus (P), arsenic (As) andantimony (Sb).

In the semiconductor device according to some example embodiments, it isassumed that the first fin-type pattern 110 and the second fin-typepattern 210 are silicon fin-type patterns including silicon.

A field insulating film 105 may be formed on the substrate 100. Thefield insulating film 105 may partially overlie the first fin-typepattern 110 and the second fin-type pattern 210. For example, the fieldinsulating film 105 may partially overlie side-walls of the firstfin-type pattern 110 and the second fin-type pattern 210. An uppersurface of the first fin-type pattern 110 and an upper surface of thesecond fin-type pattern 210 may protrude upward higher than an uppersurface of the field insulating film 105 formed adjacent to longer sidesof the first fin-type pattern 110 and the second fin-type pattern 210.The first fin-type pattern 110 and the second fin-type pattern 210 maybe defined by the field insulating film 105 on the substrate 100. Forexample, the field insulating film 105 may include at least one of asilicon oxide film, a silicon nitride film, or a silicon oxynitridefilm.

Further, the field insulating film 105 may additionally include at leastone or more field liner films formed between the first fin-type pattern110 and the field insulating film 105 and between the second fin-typepattern 210 and the field insulating film 105. When the field insulatingfilm 105 further includes the field liner film, the field liner film mayinclude at least one of polysilicon, amorphous silicon, siliconoxynitride, silicon nitride, or silicon oxide.

Referring to FIG. 2, etching process may be performed using a gate hardmask pattern 2101, such that a first dummy gate electrode 120 pextending in a third direction Y1 by intersecting the first fin-typepattern 110, and a second dummy gate electrode 220 p extending in afourth direction Y2 by intersecting the second fin-type pattern 210 areformed.

A first dummy gate insulating film 130 p may be formed between the firstfin-type pattern 110 and the first dummy gate electrode 120 p, and asecond dummy gate insulating film 230 p may be formed between the secondfin-type pattern 210 and the second dummy gate electrode 220 p.

The first dummy gate insulating film 130 p and the second dummy gateinsulating film 230 p may include, for example, one of a silicon oxide(SiO₂) film, a silicon oxynitride (SiON) film, and a combinationthereof.

The first dummy gate electrode 120 p and the second dummy gate electrode220 p may in example, polycrystalline silicon (poly Si), amorphoussilicon (a-Si), and a combination thereof. The first dummy gateelectrode 120 p and the second dummy gate electrode 220 p may not bedoped with impurities, or may be doped with similar impurities.Different from the above description, one may be doped, and the othermay not be doped. Alternatively, one may be doped with an n-typematerial (e.g., arsenic, phosphorous or other n-type materials), and theother may be doped with a p-type material (e.g., boron or other p-typematerials).

Referring to FIGS. 3 to 5, a first trench 140 t intersecting the firstfin-type pattern 110 may be formed by removing the first dummy gateelectrode 120 p and the first dummy gate insulating film 130 p. Further,by removing the second dummy gate electrode 220 p and the second dummygate insulating film 230 p, a second trench 240 t intersecting thesecond fin-type pattern 210 may be formed. On the field insulating film105, an interlayer insulating film 180 including the first trench 140 tand the second trench 240 t may be formed.

More specifically, a first gate spacer 140 and a second gate spacer 240may be respectively formed on sidewalls of the first dummy gateelectrode 120 p and the second dummy gate electrode 220 p.

A first recess 150 r may be formed by removing a portion of the firstfin-type pattern 110 which does not overlap with the first dummy gateelectrode 120 p when the first gate spacer 140 is formed. Further, asecond recess 250 r may be formed by removing a portion of the secondfin-type pattern 210 which does not overlap with the second dummy gateelectrode 220 p when the second gate spacer 240 is formed.

A first epitaxial pattern 150 for filling the first recess 150 r maythen be formed on both sides of the first dummy gate electrode 120 p.The first epitaxial pattern 150 may be included in a source/drain of thetransistor which uses the first fin-type pattern 110 as the channelregion. A second epitaxial pattern 250 for filling the second recess 250r may be formed on both sides of the second dummy gate electrode 220 p.The second epitaxial pattern 250 may be included in the source/drain ofthe transistor which uses the second fin-type pattern 210 as the channelregion.

The interlayer insulating film 180 may then be formed, to overlie efirst epitaxial pattern 150 and the second epitaxial pattern 250.Through planarization process, upper surfaces of the first dummy gateelectrode 120 p and the second dummy gate electrode 220 p may beexposed.

For example, the interlayer insulating film 180 may include siliconoxide, silicon nitride, silicon oxynitride, flowable oxide (FOX), Tonensilazene (TOSZ), undoped silica glass (USG), borosilica glass (BSG),phosphosilica glass (PSG), borophosphosilica glass (BPSG), plasmaenhanced tetra ethyl ortho silicate (PETEOS), fluoride silicate glass(FSG), carbon doped silicon oxide (CDO), xerogel, aerogel, amorphousfluorinated carbon, organo silicate glass (OSG), parylene,bis-benzocyclobutenes (BCB), SiLK, polyimide, porous polymeric material,or a combination thereof, but not limited hereto.

The first trench 140 t may be formed in the first region I and thesecond trench 240 t may be formed in the second region II, by removingthe first dummy gate electrode 120 p and the first dummy gate insulatingfilm 130 p, and removing the second dummy gate electrode 220 p and thesecond dummy gate insulating film 230 p.

The following will be described based on cross sectional views taken onlines A-A and C-C of FIG. 3, and cross sectional views taken on linesB-B and D-D of FIG. 3.

Referring to FIGS. 6 and 7, a first gate insulating film 130 may beformed along a side-wall and a bottom surface of the first trench 140 tand an upper surface of the interlayer insulating film 180. Further, asecond gate insulating film 230 may be formed along a side-wall and abottom surface of the second trench 240 t and an upper surface of theinterlayer insulating film 180.

The first gate insulating film 130 may be formed along a profile of thefirst fin-type pattern 110 protruding upward in a vertical directionhigher than an upper surface of the field insulating film 105, and alongan upper surface of the field insulating film 105. The second gateinsulating film 230 may be formed along a profile of the second fin-typepattern 210 protruding upward in a vertical direction higher than anupper surface of the field insulating film 105, and along an uppersurface of the field insulating film 105.

The first gate insulating film 130 and the second gate insulating film230 may respectively include a high-k dielectric material having ahigher dielectric constant than a silicon oxide film. For example, eachof the first gate insulating film 130 and the second gate insulatingfilm 230 may include one or more of hafnium oxide, hafnium siliconoxide, hafnium aluminum oxide, lanthanum oxide, lanthanum aluminumoxide, zirconium oxide, zirconium silicon oxide, tantalum oxide,titanium oxide, barium strontium titanium oxide, barium titanium oxide,strontium titanium oxide, yttrium oxide, aluminum oxide, lead scandiumtantalum oxide, and lead zinc niobate.

Unlike the illustration in FIGS. 6 and 7, an interfacial film may beadditionally formed between the first gate insulating film 130 and thefirst fin-type pattern 110, and between the second gate insulating film230 and the second fin-type pattern 210. When the first fin-type pattern110 and the second fin-type pattern 210 are silicon fin-type patterns,the interfacial layer may include silicon oxide, for example.

A first TaN film 121 may be formed on the first gate insulating film130. The first TaN film 121 may be formed along a profile of the firstgate insulating film 130. The first TaN film 121 may be formed on asidewall and a bottom surface of the first trench 140 t and an uppersurface of the interlayer insulating film 180. The first TaN film 121may be formed along the profile of the first fin-type pattern 110protruding upward in a vertical direction higher than the upper surfaceof the field insulating film 105, and along the upper surface of thefield insulating film 105.

A second TaN film 221 may be formed on the second gate insulating film230. The second TaN film 221 may be formed along a profile of the secondgate insulating film 230. The second TaN film 221 may be formed on aside-wall and a bottom surface of the second trench 240 t, and an uppersurface of the interlayer insulating film 180. The second TaN film 221may be formed along the profile of the second fin-type pattern 210protruding upward in a vertical direction higher than the upper surfaceof the field insulating film 105, and along the upper surface of thefield insulating film 105.

A first TiN film 122 may be formed on the first TaN film 121. The firstTiN film 122 may be formed along a profile of the first TaN film 121.The first TiN film 122 may be formed on a side-wall and a bottom surfaceof the first trench 140 t and an upper surface of the interlayerinsulating film 180. The first TiN film 122 may be formed along theprofile of the first fin-type pattern 110 protruding upward in avertical direction higher than the upper surface of the field insulatingfilm 105, and along the upper surface of the field insulating film 105.

A second TiN film 222 may be formed on the second TaN film 221. Thesecond TiN film 222 may be formed along a profile of the second TaN film221. The second TiN film 222 may be formed on a sidewall and a bottomsurface of the second trench 240 t, and an upper surface of theinterlayer insulating film 180. The second TiN film 222 may be formedalong a profile of the second fin-type pattern 210 protruding upward ina vertical direction higher than the upper surface of the fieldinsulating film 105, and along the upper surface of the field insulatingfilm 105.

Referring to FIGS. 8 and 9, a mask pattern 40 may be formed on thesecond TiN film 222.

Because the mask pattern 40 may be formed on the second region II andnot formed on the first region I, the first TiN film 122 may be exposedby the mask pattern 40. In other words, the mask pattern 40 may coverthe second TiN film 222 and may not cover the first TiN film 122.

Although the mask pattern 40 is illustrated as a single-layered film,this is provided only for convenience of explanation and exampleembodiments are not limited hereto.

Referring to FIGS. 10 and 11, the first TiN film 122 may be removedusing the mask pattern 40 with wet etching.

The wet etching 50 may be performed using the etching compositionaccording to some example embodiments described above.

For example, the first TaN film 121 may be exposed with removal of thefirst TiN film 122, but not limited hereto.

In other words, unlike illustration, a portion of the first TiN film 122may be removed by adjusting a duration of time of the wet etching.Through the above, the rest portion of the first TiN film 122 may remainon the first TaN film 121.

The mask pattern 40 on the second region II may then be removed.

Referring to FIGS. 12 and 13, a first upper electrode film 123 may beformed on the first TaN film 121, and a second upper electrode film 223may be formed on the second TiN film 222.

The first upper electrode film 123 may be formed on the upper surface ofthe interlayer insulating film 180, while filling the first trench 140t. The second upper electrode film 223 may be formed on the uppersurface of the interlayer insulating film 180, while filling the secondtrench 240 t.

The first upper electrode film 123 and the second upper electrode film223 may respectively include at least one of, for example, titaniumnitride (TiN), tantalum carbide (TaC), titanium silicon nitride (TiSiN),tantalum silicon nitride (TaSiN), tantalum titanium nitride (TaTiN),titanium aluminum nitride (TiAlN), tantalum aluminum nitride (TaAlN),tungsten nitride (WN), ruthenium (Ru), titanium aluminum (TiAl),titanium aluminum carbonitride (TiAlC—N), titanium aluminum carbide(TiAlC), titanium carbide (TiC), tantalum carbonitride (TaCN), tungsten(W), aluminum (Al), copper (Cu), cobalt (Co), titanium (Ti), tantalum(Ta), nickel (Ni), platinum (Pt), nickel platinum (Ni—Pt), niobium (Nb),niobium nitride (NbN), niobium carbide (NbC), molybdenum (Mo),molybdenum nitride (MoN), molybdenum carbide (MoC), tungsten carbide(WC), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), silver(Ag), gold (Au), zinc (Zn), vanadium (V), or a combination thereof.

Referring to FIG. 14, a first gate electrode 120 may be formed withinthe first trench 140 t by removing the first gate insulating film 130,the first TaN film 121, and the first upper electrode film 123, whichare formed on the interlayer insulating film 180.

A second gate electrode 220 may be formed within the second trench 240 tby removing the second gate insulating film 230, the second TaN film221, the second TiN film 222, and the second upper electrode film 223,which are formed on the upper surface of the interlayer insulating film180.

The first gate electrode 120 may include the first TaN film 121 and thefirst upper electrode film 123, and the second gate electrode 220 mayinclude the second TaN film 222, the second TiN film 222, and the secondupper electrode film 223.

FIGS. 15 to 25 are views illustrating intermediate stages of fabricationillustrating a method for fabricating a semiconductor device using anetching composition according to some example embodiments of presentdisclosure. FIG. 16 is a cross sectional view taken on lines E-E and G-Gof FIG. 15, and FIG. 17 is a cross sectional view taken on lines F-F andH-H of FIG. 15.

Referring to FIGS. 15 to 17, a sacrificial film 2001 and an active film2002 may be sequentially formed on the substrate 100 including the firstregion I and the second region The sacrificial film 2001 and the activefilm 2002 may be formed using, for example, an epitaxial growth method.

The active film 2002 may contain a material having etch selectivity withrespect to the sacrificial film 2001.

In FIG. 15, it is illustrated that the active film 2002 is asingle-layered film and the sacrificial film 2001 is a double-layeredfilm, but this is just for convenience sake, and example embodiments arenot limited hereto. Further, although it is illustrated that thesacrificial film 2001 is positioned on the uppermost portion, exampleembodiments are not limited hereto.

Then, on the sacrificial film 2001 of the first region I and the secondregion II a structure mask pattern 2100 may be formed respectively.

In the first region I, the structure mask pattern 2100 may extendlongitudinally in the first direction X1. In the second region II, thestructure mask pattern 2100 may extend longitudinally in the seconddirection X2.

Following will be explained based on cross sectional views taken onlines E-E and G-G of FIG. 15, and a cross sectional views taken on linesF-F and H-H of FIG. 15.

Referring to FIGS. 18 and 19, an etching process may be performed withthe structure mask pattern 2100 as mask so as to form a first fin-typestructure F1 and a second fin-type structure F2.

The first fin-type structure F1 may be formed in the first region I. Thefirst fin-type structure F1 may include a first fin-type protrusion100P, a first sacrificial pattern 111, a first active pattern 112, and afirst sacrificial pattern 111, which are layered on the substrate 100 ina sequential order.

The second fin-type structure F2 may be formed in the second region I.The second fin-type structure F2 may include a second fin-typeprotrusion 200P, a second sacrificial pattern 211, a second activepattern 212, and a second sacrificial pattern 211, which are layered onthe substrate 100 in a sequential order.

In FIG. 19, it is illustrated that all e sacrificial films on thesubstrate 100 are removed except for the sacrificial films 2001 used toform the first fin-type structure F1 and the second fin-type structureF2, but this is just for convenience sake, and example embodiments arenot limited hereto.

Then, the field insulating film 105 to overlie at least a portion of asidewall of the first fin-type structure F1 and a sidewall of the secondfin-type structure F2 may be formed on the substrate 100.

In a process of forming the field insulating film 105, the structuremask pattern 2100 may be removed.

Then, in the first region 1, the first dummy gate electrode 120 p,intersecting the first fin-type structure F1 and extending in the thirddirection Y1, may be formed.

Further, in the second region II, the second dummy gate electrode 220 p,intersecting the second fin-type structure F2 and extending in thefourth direction Y2, may be formed.

The first dummy gate electrode 120 p and the second dummy gate electrode220 p may be formed using the gate hard mask pattern 2101.

The first dummy gate insulating film 130 p and the second dummy gateinsulating film 230 p may be formed respectively between the first dummygate electrode 120 p and the first fin-type structure F1 and between thesecond dummy gate electrode 220 p and the second fin-type structure F2.

On a side-wall of the first dummy gate electrode 120 p, a first pre-gatespacer 140 p may be formed. On a sidewall of the second dummy gateelectrode 220 p, a second pre-gate spacer 240 p may be formed.

Referring to FIGS. 20 and 21, the interlayer insulating film 180,exposing an upper surface of the first dummy gate electrode 120 p and anupper surface of the second dummy gate electrode 220 p, may be formed onthe field insulating film 105.

More specifically, a portion of the first fin-type structure F1 may beremoved using the first dummy gate electrode 120 p and the firstpre-gate spacer 140 p as a mask. By doing this, the first recess 150 rmay be formed on both sides of the first dummy gate electrode 120 p andthe first pre-gate spacer 140 p.

A first inner spacer 142 may be formed between the first active pattern112 and the first fin-type protrusion 100P. The first inner spacer 142may be formed on the first active pattern 112.

Specifically, a portion of the first sacrificial pattern 111 may beremoved using etch selectivity between the first active pattern 112 andthe first sacrificial pattern 111. Then, in a region from which aportion of the first sacrificial pattern 111 has been removed, the firstinner spacer 142 may be formed.

The first epitaxial pattern 150 may be formed within the first recess150 r.

Further, a portion of the second fin-type structure F2 may be removedusing the second dummy gate electrode 220 p and the second pre-gatespacer 240 p as a mask. By doing this, the second recess 250 r may beformed on both sides of the second dummy gate electrode 220 p and thesecond pre-gate spacer 240 p.

A second inner spacer 242 may be formed between the second activepattern 212, and the second fin-type protrusion 2000. On the secondactive pattern 212, the second inner spacer 242 may be formed.

Using etch selectivity between the second active pattern 212 and thesecond sacrificial pattern 211, a portion of the second sacrificialpattern 211 may be removed. Then, in a region from which a portion ofthe second sacrificial pattern 211 has been removed, the second innerspacer 242 may be formed.

The second epitaxial pattern 250 may be formed within the second recess150 r.

Forming the first recess 150 r and forming the second recess 250 r maybe performed simultaneously, or performed through different processeseach other. Further, forming the first epitaxial pattern 150 and formingthe second epitaxial pattern 250 may be performed simultaneously, orperformed through different processes each other.

The interlayer insulating film 180 may then be formed to overlie thefirst epitaxial pattern 150 and the second epitaxial pattern 250.Through planarization process, upper surfaces of the first dummy gateelectrode 120 p and the second dummy gate electrode 220 p may beexposed.

While the interlayer insulating film 180 is being formed, each of afirst outer spacer 141 and a second outer spacer 241 may be formed.

Referring to FIGS. 22 and 23, as the first dummy gate electrode 120 p,the first dummy gate insulating film 130 p, and the first sacrificialpattern 111 are removed, a first wire pattern 115 may be formed on thesubstrate 100 of the first region I.

Further, as the second dummy gate electrode 220 p, the second dummy gateinsulating film 230 p, and second sacrificial pattern 211 are removed, asecond wire pattern 215 may be formed on the substrate 100 of the secondregion

The first wire pattern 115 may be formed with spacing from the firstfin-type protrusion 100P, and the second wire pattern 215 may be formedwith spacing from the second fin-type protrusion 200P.

Further, as the first dummy gate electrode 120 p, the first dummy gateinsulating film 130 p, and the first sacrificial pattern 111 areremoved, the first trench 140 t may be formed being defined by the firstgate spacer 140. The first trench 140 t may intersect the first wirepattern 115.

Further, as the second dummy gate electrode 220 p, the second dummy gateinsulating film 230 p, and the second sacrificial pattern 211 areremoved, the second trench 240 t may be formed being defined by thesecond gate spacer 240. The second trench 240 t may intersect the secondwire pattern 215.

The first gate spacer 140 may include the first inner spacer 142 and thefirst outer spacer 141. The second gate spacer 240 may include thesecond inner spacer 242 and the second outer spacer 241.

Referring to FIGS. 24 and 25, the first gate insulating film 130 may beformed along the sidewall and the bottom surface of the first trench 140t and the upper surface of the interlayer insulating film 180. Further,a second gate insulating film 230 may be formed along a sidewall and abottom surface of the second trench 240 t and an upper surface of theinterlayer insulating film 180.

The first gate insulating film 130 may be formed along a perimeter ofthe first wire pattern 115, and the upper surface of the fieldinsulating film 105. The second gate insulating film 230 may be formedalong a perimeter of the second wire pattern 215, and the upper surfaceof the field insulating film 105.

The first TaN film 121 may be formed on the first gate insulating film130. The first TaN film 121 may be formed along a profile of the firstgate insulating film 130. The first TaN film 121 may be formed on asidewall and a bottom surface of the first trench 140 t and an uppersurface of the interlayer insulating film 180. The first TaN film 121may be formed along a perimeter of the first wire pattern 115 and theupper surface of the field insulating film 105.

The second TaN film 221 may be formed on the second gate insulating film230. The second TaN film 221 may be formed along a profile of the secondgate insulating film 230. The second TaN film 221 may be formed on asidewall and a bottom surface of the second trench 240 t and an uppersurface of the interlayer insulating film 180. The second TaN film 221may be formed along a perimeter of the second wire pattern 215 and theupper surface of the field insulating film 105.

The first TiN film 122 may be formed on the first TaN film 121. Thefirst TiN film 122 may be formed along a profile of the first TaN film121. The first TiN film 122 may be formed on a side-wall and a bottomsurface of the first trench 140 t and an upper surface of the interlayerinsulating film 180. The first TiN film 122 may be formed along theperimeter of the first wire pattern 115 and the upper surface of thefield insulating film 105.

A second TiN film 222 may be formed on the second TaN film 221. Thesecond TiN film 222 may be formed along a profile of the second TaN film221. The second TiN film 222 may be formed on a sidewall and a bottomsurface of the second trench 240 t and an upper surface of theinterlayer insulating film 180. The second TiN film 222 may be formedalong the perimeter of the second wire pattern 215 and the upper surfaceof the field insulating film 105.

Through the processes described with reference to FIGS. 8 to 11, thefirst TiN film 122 may be removed.

The gate electrode intersecting the first wire pattern 115 may be formedby filling the first trench 140 t with a conductive material. Further,the gate electrode intersecting the second wire pattern 215 may beformed by filling the second trench 240 t with a conductive material.

In concluding the detailed description, those skilled in the art willappreciate that many variations and modifications can be made to exampleembodiments without substantially departing from the principles of thepresent disclosure. Therefore, the disclosed example embodiments of theinventive concepts are used in a generic and descriptive sense only andnot for purposes of limitation.

1. An etching composition having an etching selectivity for titaniumnitride (TiN), the etching composition comprising: 5 wt % to 30 wt % ofhydrogen peroxide, 15 wt % to 50 wt % of an acid compound, and 0.001 wt% to 5 wt % of a corrosion inhibitor, with respect to a total weight ofthe etching composition, wherein the acid compound includes at least oneof phosphoric acid (H₃PO₄), nitric acid (HNO₃), hydrochloric acid (HCl),hydroiodic acid (HI), hydrobromic acid (HBr), perchloric acid (HClO₄),silicic acid (H₂SiO₃), boric acid (H₃BO₃), acetic acid (CH₃COOH),propionic acid (C₂H₅COOH), lactic acid (CH₃CH(OH)COOH), and glycolicacid (HOCH₂COOH).
 2. The etching composition of claim 1, wherein theacid compound comprises phosphoric acid.
 3. The etching composition ofclaim 1, wherein the corrosion inhibitor comprises at least one ofammonium peroxysulfate, ammonium sulfate, monoammonium phosphate,diammonium phosphate, triammonium phosphate, ammonium chloride, ammoniumacetate, ammonium carbonate, ammonium nitrate, ammonium iodide,1,2,4-triazole, 3-aminotriazole, 5-aminotetrazole, benzotriazole,pyrazole, imidazole, ascorbic acid, citric acid, succinic acid, maleicacid, malonic acid, thioglycolic acid, tannic acid, methyl gallate,ethyl gallate, and propyl gallate.
 4. The etching composition of claim1, further comprising: 0.001 wt % to 5 wt % of a chelating agent withrespect to the total weight of the etching composition, wherein thechelating agent comprises at least one of ethylenediaminetetraaceticacid, iminodiacetic acid, diethylenetriaminepentaacetic acid, glycine,alanine, valine, leucine, isoleucine, serine, threonine, tyrosine,phenylalanine, tryptophane, aspartic acid, glutamic acid, glutamine,asparagine, lysine, arginine, histidine, hydroxylysine, cysteine,methionine, cystine, proline, sulfamic acid, and hydroxyproline.
 5. Theetching composition of claim 1, further comprising: 0.001 wt % to 0.1 wt% of a surfactant with respect to the total weight of the etchingcomposition, wherein the surfactant comprises at least one of alkylsulfonate, ammonium alkyl sulfonate, alkyl ether sulfonate, alkyl arylether sulfonate, alkyl phosphate, ammonium alkyl phosphate, alkyl etherphosphate, alkyl aryl ether phosphate, fluoroalkyl sulfonimide, ammoniumfluoroalkyl sulfonimide, C_(n)H_(2n+1)CH₂CH₂SO₃—NH₄+,CH_(2n+1)CH₂CH₂SO₃H,(C_(n)H_(2n+1)CH₂CH₂O)_(x)PO(ONH₄+)_(y)(OCH₂CH₂OH)_(z),C_(n)H_(2n+1)CH₂CH₂O(OCH₂CH₂OH)_(x)H,C_(n)H_(2n+1)SO₂N(C₂H₅)(CH₂CH₂)_(x)H,CH_(2n+1)CH₂CH₂OCH₂(OH)CH₂CH₂N(C_(n)H_(2n+1))₂,C_(n)H_(2n+1)CH₂CH₂OCH₂(OCH₂CH₂)_(n)CH₂CH₂N(C_(n)H_(2n+1))₂,C_(n)F_(2n+1)CH₂CH₂SO₃—NH₄+, C_(n)F_(2n+1)CH₂CH₂SO₃H,(C_(n)F_(2n+1)CH₂CH₂O)_(x)PO(ONH₄+)_(y)(OCH₂CH₂OH)_(z),C_(n)F_(2n+1)CH₂CH₂O(OCH₂CH₂OH)_(x)H,C_(n)F_(2n+1)SO₂N(C₂H₅)(CH₂CH₂)_(x)H,C_(n)F_(2n+1)CH₂CH₂OCH₂(OH)CH₂CH₂N(C_(n)F_(2n+1))₂, andC_(n)F_(2n+1)CH₂CH₂OCH₂(OCH₂CH₂)_(n)CH₂CH₂N(C_(n)F_(2n+1))₂, where, n isan integer between 1 to 20, when x, y and z are present simultaneously,x, y, and z are real numbers satisfying x+y+z=3, and when x is presentalone, x is an integer of 1 to
 3. 6. The etching composition of claim 1,wherein a pH of the etching composition is equal to or less than
 2. 7.The etching composition of claim 1, wherein the etching composition hasa selectivity for removing a titanium nitride film of a stacked filmincluding the titanium nitride film and a tantalum nitride film.
 8. Theetching composition of claim 7, wherein an etch selectivity of thetitanium nitride film with respect to the tantalum nitride film is equalto or greater than
 500. 9. The etching composition of claim 1, furthercomprising: deionized water (DIW) as a remainder of the etchingcomposition.
 10. An etching composition having an etching selectivityfor titanium nitride (TiN), comprising hydrogen peroxide, an acidcompound, and a corrosion inhibitor, wherein a ratio of a weight of theacid compound with respect to a weight of the hydrogen peroxide is from1 to 7, and the acid compound comprises at least one of phosphoric acid(H₃PO₄), nitric acid (HNO₃), hydrochloric acid (HCl), hydroiodic acid(HI), hydrobromic acid (HBr), perchloric acid (HClO₄), silicic acid(H₂SiO₃), boric acid (H₃BO₃), acetic acid (CH₃COOH), propionic acid(C₂H₅COOH), lactic acid (CH₃CH(OH)COOH), and glycolic acid (HOCH₂COOH).11. The etching composition of claim 10, wherein the acid compound isH₃PO₄.
 12. The etching composition of claim 10, wherein the etchingcomposition comprises 5 wt % to 30 wt % of the hydrogen peroxide and 15wt % to 50 wt % of the acid compound, with respect to a total weight ofthe etching composition.
 13. The etching composition of claim 10,wherein the etching composition has a selectivity for removing atitanium nitride film from a stacked film of the titanium nitride filmand a tantalum nitride film, and an etch selectivity of the titaniumnitride film with respect to the tantalum nitride film is equal to orgreater than
 500. 14. The etching composition of claim 10, furthercomprising: at least one of a chelating agent and a surfactant. 15-21.(canceled)
 22. An etching composition comprising: 5 wt % to 30 wt % ofhydrogen peroxide, 15 wt % to 50 wt % of an acid compound, and 0.001 wt% to 5 wt % of a corrosion inhibitor, with respect to a total weight ofthe etching composition, wherein the corrosion inhibitor is at least oneof ammonium peroxysulfate, ammonium sulfate, monoammonium phosphate,diammonium phosphate, triammonitun phosphate, ammonium chloride,ammonium acetate, ammonium carbonate, ammonium nitrate, ammonium iodide,1,2,4-triazole, 3-aminotriazole, 5-aminotetrazole, benzotriazole,pyrazole, imidazole, ascorbic acid, citric acid, succinic acid, maleicacid, malonic acid, thioglycolic acid, tannic acid, methyl gallate,ethyl gallate, and propyl gallate.
 23. The etching composition of claim22, wherein the acid compound comprises phosphoric acid.
 24. The etchingcomposition of claim 22, further comprising: 0.001 wt % to 5 wt % of achelating agent with respect to the total weight of the etchingcomposition, wherein the chelating agent comprises at least one ofethylenediaminetetraacetic acid, iminodiacetic acid,diethylenetriaminepentaacetic acid, glycine, alanine, valine, leucine,isoleucine, serine, threonine, tyrosine, phenylalanine, tryptophane,aspartic acid, glutamic acid, glutamine, asparagine, lysine, arginine,histidine, hydroxylysine, cysteine, methionine, cystine, proline,sulfamic acid, and hydroxyproline.
 25. (canceled)
 26. The etchingcomposition of claim 22, wherein a pH of the etching composition isequal to or less than
 2. 27. The etching composition of claim 22,further comprising: deionized water (DIW) as a remainder of the etchingcomposition.
 28. The etching composition of claim 22, wherein the acidcompound does not include a sulfur-based compound.